Butene-1 polymer composition having high melt flow rate

ABSTRACT

A butene-1 polymer composition having a MFR value of from 100 to 300 g/10 min., measured according to ISO 1133 at 190° C. with a load of 2.16 kg, made from or containing:
     A) a butene-1 homopolymer or a copolymer of butene-1 with one or more comonomers selected from the group consisting of ethylene and higher alpha-olefins, having a copolymerized comonomer content of up to 5% by mole;   B) a copolymer of butene-1 with one or more comonomers selected from the group consisting of ethylene and higher alpha-olefins, having a copolymerized comonomer content of from 6% to 20% by mole;
 
wherein the composition having a total copolymerized comonomer content from 4% to 15% by mole, referred to the sum of A) and B), and a content of fraction soluble in xylene at 0° C. of 75% by weight or less, determined on the total weight of A) and B).

FIELD OF THE INVENTION

In general, the present disclosure relates to the field of chemistry.More specifically, the present disclosure relates to polymer chemistry.In particular, the present disclosure relates to a butene-1 polymercomposition as well as films, fibers, hot-melt adhesives, polymeradditives, and fluidizers made therefrom.

BACKGROUND OF THE INVENTION

Butene-1 polymers having high melt flow rate have been used in manyapplication fields. In those applications, the utility of the butene-1polymers is believed due to properties such as chemical inertia,mechanical properties and nontoxicity.

In some instances, the molecular weights and molecular weightdistribution of the butene-1 polymer have an effect on the final polymerproperties.

SUMMARY OF THE INVENTION

In a general embodiment, the present disclosure provides a butene-1polymer composition having a Melt Flow Rate value of from 100 to 300g/10 min., alternatively from 110 to 300 g/10 min., alternatively from150 to 250 g/10 min., measured according to ISO 1133 at 190° C. with aload of 2.16 kg (hereinafter called “MFR”) and made from or containing:

-   -   A) a butene-1 homopolymer or a copolymer of butene-1 with one or        more comonomers selected from the group consisting of ethylene        and higher alpha-olefins, having a copolymerized comonomer        content (C_(A)) of up to 5% by mole, alternatively up to 4% by        mole; and    -   B) a copolymer of butene-1 with one or more comonomers selected        from the group consisting of ethylene and higher alpha-olefins,        having a copolymerized comonomer content (C_(B)) of from 6% to        20% by mole, alternatively from 8% to 18% by mole;        wherein the composition having a total copolymerized comonomer        content from 4% to 15% by mole, alternatively from 5% to 15% by        mole, referred to the sum of A) and B), and a content of        fraction soluble in xylene at 0° C. of 75% by weight or less,        alternatively of 70% by weight or less, determined on the total        weight of A) and B).

In some embodiments, the butene-1 polymer composition is obtaineddirectly in polymerization in the absence of free radical generatingagents like peroxides, thereby increasing the MFR value and avoiding thechemical contamination and unpleasant odor which results from theintroduction of free radical generating agents.

In some embodiments, the present butene-1 polymer composition is blendedwith other polyolefins, alternatively propylene polymers. In someembodiments, the butene-1 polymer is used in films, fibers, and hot meltcompositions.

DETAILED DESCRIPTION OF THE INVENTION

In some embodiments, the amount of fraction soluble in xylene at 0° C.for the butene-1 polymer composition, expressed as the weight content offraction measured by extraction on the total weight of A) and B), isfrom 35% to 75% by weight, alternatively from 35% to 70% by weight,alternatively from 40% to 70% by weight, alternatively from 40% to 65%by weight.

When A) is a copolymer, a specific lower limit of comonomer content isof 1% by mole.

In some embodiments, when both A) and B) are copolymers, the differencebetween the percent values of the copolymerized comonomer contents of B)and A) satisfies the following relation:

C _(B))−C _(A))≥5; alternatively C _(B))−C _(A))≥6.

In some embodiments, the relative amounts of components A) and B) aredetermined depending upon the total copolymerized comonomer content, thecomonomer contents of the single components and their content offraction soluble in xylene at 0° C.

In some embodiments, the amounts are from 30% to 70% by weight,alternatively from 35% to 65% by weight of A) and from 30% to 70% byweight, alternatively from 35% to 75% by weight of B), the weightpercents are in reference to the total weight of A) and B).

In some embodiments, the higher alpha-olefins have the formula CH₂=CHRwherein R is methyl or an alkyl radical containing 3 to 8 or 3 to 6carbon atoms. In some embodiments, the higher alpha-olefins are selectedfrom the group consisting of propylene, hexene-1, and octene-1.

In some embodiments, ethylene is the comonomer. In some embodiments,ethylene is the comonomer for component B).

The present butene-1 polymer composition has a measurable crystallinity,as demonstrated by the presence, in the Differential Scanningcalorimetry (DSC) pattern, of the melting temperature peaks ofcrystalline butene-1 polymers.

In some embodiments, the present butene-1 polymer shows one or moremelting peaks in the second DSC heating scan. In some embodiments, thetemperature peak or peaks occurring at temperatures equal to or lowerthan 90° C., alternatively equal to or lower than 85° C., alternativelyfrom 40° C. to 90° C., alternatively from 45° C. to 85° C. It isbelieved that such temperature peaks are attributed to the melting pointof crystalline form II of the butene-1 polymers (TmII) and the areaunder the peak (or peaks) is taken as the global melting enthalpy (DHTmII). However, if more than one peak is present, the highest (mostintense) peak is taken as TmII.

In some embodiments, global DH TmII values for the present butene-1polymer are of 15 J/g or less, alternatively from 4 to 15 J/g, measuredwith a scanning speed corresponding to 10° C./min.

In some embodiments, the present butene-1 polymer shows one or moremelting peaks occurring at temperatures equal to or lower than 100° C.,alternatively equal to or lower than 98° C., alternatively from 30° C.to 100° C., alternatively from 30° C. to 98° C., in a DSC heating scancarried out after aging. It is believed that such temperature peak orpeaks are attributed to the melting point of crystalline form I of thebutene-1 polymers (TmI) and the area under the peak (or peaks) is takenas the global melting enthalpy (DH TmI). However, if more than one peakis present, the highest (most intense) peak is taken as TmI.

In some embodiments, global DH TmI values for the present butene-1polymer are of 50 J/g or less, alternatively from 25 to 50 J/g,alternatively from 30 to 50 J/g, measured with a scanning speedcorresponding to 10° C./min.

In some embodiments, the present butene-1 polymer has a detectablecontent of crystalline form III. Crystalline form III is detectable viathe X-ray diffraction method described in the Journal of Polymer SciencePart B: Polymer Letters Volume 1, Issue 11, pages 587-591, November1963, or Macromolecules, Vol. 35, No. 7, 2002.

In some embodiments, X-ray crystallinity values for the present butene-1polymer are from 10% to 50%, alternatively from 15% to 45%.

In some embodiments, the MFR values for components A) and B) are broadlyselected, provided that the MFR values of the overall composition areobtained.

The logarithm of the MFR value of polyolefin blends is given by the sumof the products of the weight fraction and the logarithm of the MFRvalue of the single components.

Therefore, the MFR value of a composition made of a blend of componentsA) and B) is determined by the following relation:

log MFR (A+B)=wA log MFR (A)+wB log MFR (B)

where MFR (A+B) is the MFR value for the blend of A) and B), MFR (A) andMFR (B) are the MFR values of components A) and B) respectively and wAand wB are the respective weight fractions. For instance, wA and wB areboth 0.5 when the blend is made of 50% by weight of component A) and 50%by weight of component B).

In some embodiments and to achieve good fluidity in the molten state,the MFR values of the single components A) and B) are in the range offrom 50 to 400 g/10 min., alternatively from 80 to 350 g/10 min.

In some embodiments, the present butene-1 polymer composition has atleast one of the following further features:

-   -   an intrinsic viscosity (IV) measured in tetrahydronaphthalene        (THN) at 135° C. equal to lower than 0.70 dl/g, alternatively        equal to or lower than 0.65 dl/g, alternatively from 0.50 dl/g        to 0.70 dl/g, alternatively from 0.50 dl/g to 0.65 dl/g;    -   a Mw/Mn value, where Mw is the weight average molar mass and Mn        is the number average molar mass, both measured by GPC (Gel        Permeation Chromatography), equal to or lower than 3.5,        alternatively equal to or lower than 2.5, the lower limit being        of 1.5 for the ranges;    -   a Mz value of 90,000 g/mol or higher, alternatively of 100,000        g/mol or higher, alternatively from 90,000 to 200,000 g/mol,        alternatively from 100,000 to 190,000 g/mol;    -   Mw equal to or greater than 50,000 g/mol, alternatively equal to        or greater than 70,000 g/mol, alternatively from 50,000 to        180,000 g/mol, alternatively from 70,000 to 150,000 g/mol;    -   isotactic pentads (mmmm) measured with ¹³C-NMR operating at        150.91 MHz higher than 90%; alternatively higher than 93%,        alternatively higher than 95%;    -   4,1 insertions not detectable using a ¹³C-NMR operating at        150.91 MHz;    -   a yellowness index lower than 0; alternatively from 0 to −10,        alternatively from −1 to −9, alternatively from −1 to −5;    -   a Shore D value equal to or lower than 50, alternatively equal        to or lower than 45, alternatively from 15 to 50, alternatively        from 15 to 45;    -   a tensile stress at break, measured according to ISO 527, of        from 10 MPa to 45 MPa, alternatively from 10 MPa to 35 MPa;    -   a tensile elongation at break, measured according to ISO 527, of        from 400% to 900%; alternatively from 450% to 700%;    -   a glass transition temperature of −19° C. or less, alternatively        of −20° C. or less, wherein the lower limit is −23° C.    -   a density of 0.880 g/cm³ or more, alternatively 0.885 g/cm³ or        more; wherein the upper limit is of 0.910 g/cm³, alternatively        of 0.899 g/cm³.

In some embodiments, the butene-1 polymer components A) and B) areobtained by polymerizing the monomer(s) in the presence of a metallocenecatalyst system obtainable by contacting:

-   -   a stereorigid metallocene compound;    -   an alumoxane or a compound capable of forming an alkyl        metallocene cation; and, optionally,    -   an organo aluminum compound.

In some embodiments, the stereorigid metallocene compound belongs to thefollowing formula (I):

wherein:M is an atom of a transition metal selected from those belonging togroup 4; alternatively M is zirconium;X, equal to or different from each other, is a hydrogen atom, a halogenatom, a R, OR, OR′O, OSO₂CF₃, OCOR, SR, NR₂ or PR₂ group wherein R is alinear or branched, saturated or unsaturated C₁-C₂₀-alkyl,C₃-C₂₀-cycloalkyl, C₆-C₂₀-aryl, C₇-C₂₀-alkylaryl or C₇-C₂₀-arylalkylradical, optionally containing heteroatoms belonging to groups 13-17 ofthe Periodic Table of the Elements; and R′ is a C₁-C₂₀-alkylidene,C₆-C₂₀-arylidene, C₇-C₂₀-alkylarylidene, or C₇-C₂₀-arylalkylideneradical; alternatively X is a hydrogen atom, a halogen atom, a OR′O or Rgroup; alternatively X is chlorine or a methyl radical;R¹, R², R⁵, R⁶, R⁷, R⁸ and R⁹, equal to or different from each other,are hydrogen atoms, or linear or branched, saturated or unsaturatedC₁-C₂₀-alkyl, C₃-C₂₀-cycloalkyl, C₆-C₂₀-aryl, C₇-C₂₀-alkylaryl orC₇-C₂₀-arylalkyl radicals, optionally containing heteroatoms belongingto groups 13-17 of the Periodic Table of the Elements; in someembodiments, R⁵ and R⁶, and/or R⁸ and R⁹ form a saturated orunsaturated, 5 or 6 membered rings; in some embodiments, the ring bearsC₁-C₂₀ alkyl radicals as substituents; with the proviso that at leastone of R⁶ or R⁷ is a linear or branched, saturated or unsaturatedC₁-C₂₀-alkyl radical, optionally containing heteroatoms belonging togroups 13-17 of the Periodic Table of the Elements; alternatively aC₁-C₁₀-alkyl radical;R³ and R⁴, equal to or different from each other, are linear orbranched, saturated or unsaturated C₁-C₂₀-alkyl radicals, optionallycontaining heteroatoms belonging to groups 13-17 of the Periodic Tableof the Elements; alternatively R³ and R⁴ equal to or different from eachother are C₁-C₁₀-alkyl radicals; alternatively R³ is a methyl, or ethylradical; and R⁴ is a methyl, ethyl or isopropyl radical.

In some embodiments, the compounds of formula (I) have formula (Ia):

wherein:M, X, R¹, R², R⁵, R⁶, R⁸ and R⁹ are as described above;R³ is a linear or branched, saturated or unsaturated C₁-C₂₀-alkylradical, optionally containing heteroatoms belonging to groups 13-17 ofthe Periodic Table of the Elements; alternatively R³ is a C₁-C₁₀-alkylradical; alternatively R³ is a methyl, or ethyl radical.

In some embodiments, the metallocene compounds are selected from thegroup consisting ofdimethylsilyl{(2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride;dimethylsilanediyl{(1-(2,4,7-trimethylindenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}Zirconiumdichloride anddimethylsilanediyl{(1-(2,4,7-trimethylindenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconiumdimethyl.

In some embodiments, the alumoxanes are selected from the groupconsisting of methylalumoxane (MAO), tetra-(isobutyl)alumoxane (TIBAO),tetra-(2,4,4-trimethyl-pentyl)alumoxane (TIOAO),tetra-(2,3-dimethylbutyl)alumoxane (TDMBAO) andtetra-(2,3,3-trimethylbutyl)alumoxane (TTMBAO).

In some embodiments, the compounds capable of forming analkylmetallocene cation are compounds of formula D⁺E⁻, wherein D⁺ is aBronsted acid, able to donate a proton and react irreversibly with asubstituent X of the metallocene of formula (I) and E⁻ is a compatibleanion, which is able to stabilize the active catalytic speciesoriginating from the reaction of the two compounds and sufficientlylabile to be able to be removed by an olefinic monomer. In someembodiments, the anion E⁻ is made from or contains one or more boronatoms.

In some embodiments, the organo aluminum compound is selected from thegroup consisting of trimethylaluminum (TMA), triisobutylaluminum (TIBA),tris(2,4,4-trimethyl-pentyl)aluminum (TIOA),tris(2,3-dimethylbutyl)aluminum (TDMBA) andtris(2,3,3-trimethylbutyl)aluminum (TTMBA).

In some embodiments, the catalyst system and polymerization processesemploying the catalyst system are as described in Patent CooperationTreaty Publication Nos. WO2004099269 and WO2009000637.

In some embodiments, the two components A) and B) of the presentbutene-1 polymer composition are prepared separately and then blendedtogether in the molten state by polymer processing apparatuses. In someembodiments, the polymer processing apparatuses are mono- and twin screwextruders.

In some embodiments, the present butene-1 polymer composition isprepared directly in polymerization.

The polymerization process for producing the composition includes atleast two sequential stages, carried out in two or more reactorsconnected in series, wherein components A) and B) are prepared inseparate subsequent stages, operating in each stage, except for thefirst stage, in the presence of the polymer formed and the catalyst usedin the preceding stage.

In some embodiments, the polymerization process is carried out in liquidphase, optionally in the presence of an inert hydrocarbon solvent, or ingas phase, using fluidized bed or mechanically agitated gas phasereactors.

In some embodiments, the catalyst is added in the first reactor, or inmore than one reactor.

In some embodiments, the hydrocarbon solvent is aromatic or aliphatic.In some embodiments, the aromatic hydrocarbon solvent is toluene. Insome embodiments, the aliphatic hydrocarbon solvent is selected from thegroup consisting of propane, hexane, heptane, isobutane, cyclohexane,2,2,4-trimethylpentane and isododecane.

In some embodiments, the polymerization process is carried out by usingliquid butene-1 as polymerization medium. In some embodiments, thepolymerization temperature is from 20° C. to 150° C., alternativelybetween 50° C. and 90° C., alternatively from 65° C. to 82° C.

In some embodiments, the concentration of hydrogen in the liquid phaseduring the polymerization reaction (molar ppm H₂/butene-1 monomer) isfrom 1000 ppm to 1900 ppm, alternatively from 1100 ppm to 1800 ppm.

In some embodiments, the amount of comonomer in the liquid phase is from0.1% to 8% by weight, alternatively from 0.2% to 6% by weight, withrespect to the total weight of comonomer and butene-1 monomer present inthe polymerization reactor. In some embodiments, the comonomer isethylene.

In some embodiments, for the preparation of component A) the amount ofcomonomer is from 0.1% to 0.9%, alternatively from 0.2% to 0.8% byweight. In some embodiments, the comonomer is from 1% to 8% by weight,alternatively from 1.5% to 6% by weight, for the preparation ofcomponent B).

In some embodiments for hot-melt adhesive applications, the presentbutene-1 polymer composition is blended with other materials.

In some embodiments, the present disclosure provides a hot-melt adhesivepolyolefin composition made from or containing one or more of thefollowing optional components, in addition to the present butene-1polymer composition made from or containing components A) and B):

I) at least one additional polymer;II) at least one resin material different from (I);III) at least one wax or oil; andIV) a nucleating agent.

In some embodiments, the additional polymer is selected from the groupconsisting of amorphous poly-alpha-olefins, thermoplastic polyurethanes,ethylene/(meth)acrylate copolymers, ethylene/vinyl acetate copolymersand mixtures thereof. In some embodiments, the resin material differentfrom (I) is selected from the group consisting of aliphatic hydrocarbonresins, terpene/phenolic resins, polyterpenes, rosins, rosin esters andderivatives thereof and mixtures thereof. In some embodiments, the waxor oil is selected from the group consisting of mineral, paraffinic ornaphthenic waxes and oils. In some embodiments, the nucleating agent isselected from the group consisting of isotactic polypropylene,polyethylene, amides, stearamides, and talc.

In some embodiments, the amounts by weight of the optional components,with respect to the total weight of the hot-melt adhesive polyolefincomposition, when present and independently from each other are:

-   -   from 0.1% to 25%, alternatively from 1% to 25% by weight of I);    -   from 10% to 75%, alternatively from 10% to 40% by weight of II);    -   from 0.1% to 50%, alternatively from 1% to 30% by weight of        III); and    -   from 0.01% to 1%, alternatively from 0.1% to 1% by weight of        IV).

In some embodiments, the components are added and blended in the moltenstate with the present butene-1 polymer composition by polymerprocessing apparatuses. In some embodiments, the polymer processingapparatuses are mono- and twin screw extruders.

In some embodiments, the hot-melt adhesive compositions are used inpaper and packaging industry, furniture manufacture, and the productionof nonwoven articles. In some embodiments, the furniture manufactureincludes edgebands, softforming applications, and paneling in highmoisture environments. In some embodiments, the edgebands are squareedges. In some embodiments, the nonwoven articles include disposablediapers. In some embodiments, the butene-1 polymer is used in films orfibers. In some embodiments, the present disclosure provides a butene-1polymer composition for use as a fluidizer for lubricants.

EXAMPLES

Various embodiments, compositions and methods as provided herein aredisclosed below in the following examples. These examples areillustrative only, and are not intended to limit the scope of theinvention.

The following analytical methods are used to characterize the polymercompositions.

Thermal Properties (Melting Temperatures and Enthalpies)

Determined by Differential Scanning calorimetry (D.S.C.) on a PerkinElmer DSC-7 instrument, as hereinafter described.

-   -   For the determination of TmII (the melting temperature measured        in the second heating run) a weighed sample (5-10 mg) obtained        from the polymerization was sealed into an aluminum pan and        heated at 200° C. with a scanning speed corresponding to 10°        C./minute. The sample was kept at 200° C. for 5 minutes to allow        a complete melting of the crystallites, thereby cancelling the        thermal history of the sample. Successively, after cooling to        −20° C. with a scanning speed corresponding to 10° C./minute,        the peak temperature was taken as the crystallization        temperature (Tc). After standing for 5 minutes at −20° C., the        sample was heated for a second time at 200° C. with a scanning        speed corresponding to 10° C./min. In this second heating run,        the peak temperature measured was taken as (TmII). If more than        one peak was present, the highest (most intense) peak was taken        as TmII. The area under the peak (or peaks) was taken as global        melting enthalpy (DH TmII).    -   The melting enthalpy and the melting temperature were also        measured after aging (without cancelling the thermal history) as        follows by using Differential Scanning calorimetry (D.S.C.) on a        Perkin Elmer DSC-7 instrument. A weighed sample (5-10 mg)        obtained from the polymerization was sealed into an aluminum pan        and heated at 200° C. with a scanning speed corresponding to 10°        C./minute. The sample was kept at 200° C. for 5 minutes to allow        a complete melting of the crystallites. The sample was then        stored for 10 days at room temperature. After 10 days the sample        was subjected to DSC, cooled to −20° C., and then the sample was        heated at 200° C. with a scanning speed corresponding to 10°        C./min. In this heating run, the peak temperature was taken as        the melting temperature (TmI). If more than one peak was        present, the highest (most intense) peak was taken as TmI. The        area under the peak (or peaks) was taken as global melting        enthalpy after 10 days (DH TmI).

MFR

Determined according to norm ISO 1133 with a load of 2.16 kg at 190° C.(standard die).

Intrinsic Viscosity

Determined according to norm ASTM D 2857 in tetrahydronaphthalene at135° C.

Density

The density of samples was measured according to ISO 1183-1 (ISO 1183-1method A “Methods for determining the density of non-cellularplastics—Part 1: Immersion method, liquid pycnometer method andtitration method”; Method A: Immersion method, for solid plastics(except for powders) in void-free form). Test specimens were taken fromcompression molded plaques conditioned for 10 days before carrying outthe density measure.

Comonomer Contents

Comonomer contents were determined via FT-IR.

The spectrum of a pressed film of the polymer was recorded in absorbancevs. wavenumbers (cm⁻¹). The following measurements were used tocalculate the ethylene content:

-   a) area (A_(t)) of the combination absorption bands between 4482 and    3950 cm⁻¹ which is used for spectrometric normalization of film    thickness.-   b) factor of subtraction (FCR_(C2)) of the digital subtraction    between the spectrum of the polymer sample and the absorption band    due to the sequences BEE and BEB (B: butene-1 units, E: ethylene    units) of the methylenic groups (CH₂ rocking vibration).-   c) Area (A_(C2,block)) of the residual band after subtraction of the    C₂PB spectrum, which comes from the sequences EEE of the methylenic    groups (CH₂ rocking vibration).

Apparatus

A Fourier Transform Infrared spectrometer (FTIR) was used.

A hydraulic press with platens heatable to 200° C. (Carver orequivalent) was used.

Method

Calibration of (BEB+BEE) Sequences

A calibration straight line was obtained by plotting % (BEB+BEE) wt vs.FCR_(C2)/A_(t). The slope G_(r) and the intercept I_(r) were calculatedfrom a linear regression.

Calibration of EEE Sequences

A calibration straight line was obtained by plotting % (EEE) wt vs.A_(C2,block)/A_(t). The slope G_(H) and the intercept I_(H) werecalculated from a linear regression.

Sample Preparation

Using a hydraulic press, a thick sheet was obtained by pressing about1.5 g of sample between two aluminum foils. If homogeneity was inquestion, a minimum of two pressing operations was performed. A smallportion was cut from the sheet to mold a film. The film thickness rangedbetween 0.1-0.3 mm.

The pressing temperature was 140±10° C.

The IR spectrum of the sample film was collected as soon as the samplewas molded.

Procedure

The instrument data acquisition parameters were as follows:

Purge time: 30 seconds minimum.Collect time: 3 minutes minimum.

Apodization: Happ-Genzel.

Resolution: 2 cm⁻¹.

Collect the IR spectrum of the sample vs. an air background.

Calculation

Calculate the concentration by weight of the BEE+BEB sequences ofethylene units:

${\% \left( {{BEE} + {BEB}} \right){wt}} = {{G_{r} \cdot \frac{{FCR}_{C2}}{A_{t}}} + I_{r}}$

Calculate the residual area (AC2,block) after the subtraction describedabove, using a baseline between the shoulders of the residual band.

Calculate the concentration by weight of the EEE sequences of ethyleneunits:

${\% ({EEE}){wt}} = {{G_{H} \cdot \frac{A_{{C2},{block}}}{A_{t}}} + I_{H}}$

Calculate the total amount of ethylene percent by weight:

%  C 2 wt = [%(Bee + BEB)wt + %(EEE)wt]

NMR Analysis of Chain Structure

¹³C NMR spectra were acquired on a Bruker AV-600 spectrometer equippedwith cryo-probe, operating at 150.91 MHz in the Fourier transform modeat 120° C.

The peak of the T_(βδ) carbon (nomenclature according to C. J. Carman,R. A. Harrington and C. E. Wilkes, Macromolecules, 10, 3, 536 (1977))was used as an internal reference at 37.24 ppm. The samples weredissolved in 1,1,2,2-tetrachloroethane-d2 at 120° C. with an 8% wt/vconcentration. Each spectrum was acquired with a 90° pulse, 15 secondsof delay between pulses and CPD to remove ¹H-¹³C coupling. About 512transients were stored in 32K data points using a spectral window of9000 Hz.

The assignments of the spectra, the evaluation of triad distribution andthe composition were made according to Kakugo [M. Kakugo, Y. Naito, K.Mizunuma and T. Miyatake, Macromolecules, 16, 4, 1160 (1982)] andRandall [J. C. Randall, Macromol. Chem Phys., C30, 211 (1989)] using thefollowing:

BBB=100(T _(ββ))/S=I5

BBE=100T _(βδ) /S=I4

EBE=100P _(δδ) /S=I14

BEB=100S _(ββ) /S=I13

BEE=100S _(αδ) /S=I7

EEE=100(0.25S _(γδ)+0.5S _(δδ))/S=0.25I9+0.5I10

Area Chemical Shift Assignments Sequence 1 40.40-40.14 Sαα BBBB 2 39.64Tδδ EBE 39-76-39.52 Sαα BBBE 3 39.09 Sαα EBBE 4 37.27 Tβδ BBE 535.20-34.88 Tββ BBB 6 34.88-34.49 Sαγ BBEB + BEBE 7 34.49-34.00 SαδEBEE + BBEE 8 30.91 Sγγ BEEB 9 30.42 Sγδ BEEE 10 29.90 Sδδ EEE 1127.73-26.84 Sβδ + 2B₂ BBB + BBE EBEE + BBEE 12 26.70 2B₂ EBE 1324.54-24.24 Sββ BEB 14 11.22 Pδδ EBE 15 11.05 Pβδ BBE 16 10.81 Pββ BBB

To a first approximation, the mmmm was calculated using 2B2 carbons asfollows:

Area Chemical shift assignments B1  28.2-27.45 mmmm B2 27.45-26.30

mmmm=B ₁*100/(B ₁ +B ₂−2*A ₄ −A ₇ −A ₁₄)

Mw/Mn and Mz Determination by GPC

Measured by way of Gel Permeation Chromatography (GPC) in1,2,4-trichlorobenzene (TCB). Molecular weight parameters (Mn, Mw, Mz)and molecular weight distributions Mw/Mn for the samples were measuredby using a GPC-IR apparatus by PolymerChar, which was equipped with acolumn set of four PLgel Olexis mixed-bed (Polymer Laboratories) and anIR5 infrared detector (PolymerChar). The dimensions of the columns were300×7.5 mm and their particle size was 13 μm. The mobile phase flow ratewas kept at 1.0 mL/min. The measurements were carried out at 150° C.Solution concentrations were 2.0 mg/mL (at 150° C.) and 0.3 g/L of2,6-di-tert-butyl-p-cresol were added to prevent degradation. For GPCcalculation, a universal calibration curve was obtained using 12polystyrene (PS) reference samples supplied by PolymerChar (peakmolecular weights ranging from 266 to 1220000). A third-order polynomialfit was used to interpolate the experimental data and obtain therelevant calibration curve. Data acquisition and processing were done byusing Empower 3 (Waters). The Mark-Houwink relationship was used todetermine the molecular weight distribution and the relevant averagemolecular weights: the K values were K_(PS)=1.21×10⁴ dL/g andK_(PB)=1.78×10⁴ dL/g for PS and polybutene (PB) respectively, while theMark-Houwink exponents α=0.706 for PS and α=0.725 for PB were used.

For butene/ethylene copolymers, the composition of each sample wasassumed constant in the whole range of molecular weight and the K valueof the Mark-Houwink relationship was calculated using a linearcombination as reported below:

K _(EB) =x _(E) K _(PE) +x _(B) K _(PB)

where K_(EB) is the constant of the copolymer, K_(PE) (4.06×10⁻⁴, dL/g)and K_(PB) (1.78×10⁴ dL/g) are the constants of polyethylene (PE) andPB, x_(E) and x_(B) are the ethylene and the butene weight relativeamount with x_(E)+x_(B)=1. The Mark-Houwink exponents α=0.725 was usedfor the butene/ethylene copolymers independently on the composition. Endprocessing data treatment was fixed for the samples to include fractionsup at 1000 in terms of molecular weight equivalent. Fractions below 1000were investigated via GC.

Fractions Soluble and Insoluble in Xylene at 0° C. (XS−0° C.)

2.5 g of polymer composition and 250 cm³ of o-xylene were introducedinto a glass flask equipped with a refrigerator and a magnetic stirrer.The temperature was raised in 30 minutes up to the boiling point of thesolvent. The obtained clear solution was then kept under reflux andstirring for further 30 minutes. The closed flask was then cooled to100° C. in air for 10 to 15 minutes under stirring and then kept for 30minutes in thermostatic water bath at 0° C. for 60 minutes. The formedsolid was filtered on quick filtering paper at 0° C. 100 cm³ of thefiltered liquid was poured in a pre-weighed aluminum container which washeated on a heating plate under nitrogen flow, to remove the solvent byevaporation. The percent by weight of polymer soluble (Xylene Solublesat 0° C.=XS 0° C.) was calculated from the average weight of theresidues. The insoluble fraction in o-xylene at 0° C. (xylene Insolublesat 0° C.=XI %0° C.) was:

XI%0° C.=100−XS%0° C.

Determination of X-Ray Crystallinity

The X-ray crystallinity was measured with an X-ray Diffraction PowderDiffractometer (XDPD) that uses the Cu-Kα1 radiation with fixed slitsand able to collect spectra between diffraction angle 2Θ=5° and 2Θ=35°with step of 0.1° every 6 seconds. The samples were diskettes of about1.5-2.5 mm of thickness and 2.5-4.0 cm of diameter made by compressionmolding. The diskettes were aged at room temperature (23° C.) for 96hours. After this preparation the specimen was inserted in the XDPDsample holder. The XRPD instrument was set to collect the XRPD spectrumof the sample from diffraction angle 2Θ=5° to 2Θ=35° with steps of 0.1°by using counting time of 6 seconds, and at the end the final spectrumwas collected.

Ta was defined as the total area between the spectrum profile and thebaseline expressed in counts/sec·2Θ. Aa was defined as the totalamorphous area expressed in counts/sec·2Θ. Ca was defined as the totalcrystalline area expressed in counts/sec·2Θ.

The spectrum or diffraction pattern was analyzed in the following steps:

-   -   1) define a linear baseline for the whole spectrum and calculate        the total area (Ta) between the spectrum profile and the        baseline;    -   2) define an amorphous profile, along the whole spectrum, that        separate, the amorphous regions from the crystalline ones        according to the two phase model;    -   3) calculate the amorphous area (Aa) as the area between the        amorphous profile and the baseline;    -   4) calculate the crystalline area (Ca) as the area between the        spectrum profile and the amorphous profile as Ca=Ta−Aa; and    -   5) calculate the degree of crystallinity (% Cr) of the sample        using the formula:

% Cr=100×Ca/Ta

Flexural Modulus

According to norm ISO 178, measured 10 days after molding.

Shore D

According to norm ISO 868, measured 10 days after molding.

Tensile Stress and Elongation at Break

According to norm ISO 527 on compression molded plaques, measured 10days after molding.

Glass Transition Temperature Via DMTA (Dynamic Mechanical ThermalAnalysis)

Molded specimens of 76 mm by 13 mm by 1 mm were fixed to a DMTA machinefor tensile stress. The frequency of the tension was fixed at 1 Hz. TheDMTA translated the elastic response of the specimen starting from −100°C. to 130° C. The elastic response was plotted versus temperature. Theelastic modulus for a viscoelastic material was defined as E=E′+iE“. Insome instances, the DMTA split the two components E′ and E” by resonanceand plotted E′ vs temperature and E′/E″=tan (δ) vs temperature.

The glass transition temperature Tg was assumed to be the temperature atthe maximum of the curve E′/E″=tan (δ) vs temperature.

Yellowness Index

Determined accordingly to ASTM D1925.

Example 1 and Comparative Example 1

Preparation of the Metallocene Catalyst (A-1)

Dimethylsilyl{(2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene)}zirconium dichloride (A-1) was prepared according to Example 32 ofPatent Cooperation Treaty Publication No. WO0147939.

Preparation of the Catalytic Solution

Under nitrogen atmosphere, 8.1 L of a solution of 4.5% wt/v of TIBA inisododecane (1.84 mol of TIBA) and 760 mL of a solution 30% wt/wt of MAOin toluene (3.65 moles of MAO) were loaded in a 20 L jacketed glassreactor equipped with an anchor stirrer and allowed to react at roomtemperature for about 1 hour under stirring.

After this time, the metallocene A-1 (1.6 g, 2.75 mmol) was added anddissolved under stirring for about 30 minutes.

The final solution was discharged from the reactor into a cylinderthrough a filter to remove solid residues (if any).

The composition of the solution was as follows:

Al Zr Al/Zr Metallocene g/L % w mol ratio Conc. mg/L 16.7 0.028 1996 181

Polymerization

The polymerization was carried out continuously in a pilot plantincluding two stirred reactors connected in series in which liquidbutene-1 constituted the liquid medium.

The catalytic solution was fed in both reactors.

The polymerization conditions are reported in Table 1.

TABLE 1 Ex. 1 Operative conditions (first reactor) Temperature (° C.) 75H₂ in liquid phase 1540 (ppm mol) C₂H₄ in liquid phase 0.36 (weight %)Mileage (kg/gMe) 2777 Split (weight %) 42 C₂H₄ content of A) 0.9 (weight%) C₂H₄ content of A) 1.8 (mole %) Operative conditions (second reactor)Temperature (° C.) 75 H₂ in liquid phase 1560 (ppm mol) C₂H₄ in liquidphase 4.1 (weight %) Split (weight %) 58 C₂H₄ content of B) 6.4 (weight%) C₂H₄ content of B) 12 (mole %) Total mileage 2747 Total C₂H₄ content7.7 (mole %) Note: C₂H₄ = ethylene; kg/g Me = kilograms of polymer pergram of metallocene catalyst (A-1); Split = amount of polymer producedin the concerned reactor.

In Table 2 the properties of the final products are specified.

Table 2 reports also the properties of the butene-1 polymer taken ascomparison (Comparative Example 1), which was a commercial copolymercontaining 6.8% by mole of ethylene, prepared with a Ziegler-Nattacatalyst and subsequently subjected to a peroxide treatment.

TABLE 2 Ex. 1 Comp. 1 MFR 190° 2.16 Kg g/10 min 210 200 IntrinsicViscosity dl/g 0.61 0.69 C₂H₄ IR mol % 7.7 6.8 TmII ° C. 83.4 81.4 DHTmII J/g 11.7 16.5 TmI ° C. 93 92.5 DH TmI J/g 40.2 40.4 X - Raycrystallinity % 34 38 Xylene Soluble at 0° C. % 55.7 63.4 Mw g/mol 8790388370 Mn g/mol 40726 28182 Mw/Mn 2.2 3.1 Mz g/mol 149487 148561 Densityg/cm³ 0.898 0.899 Flexural Modulus MPa 130 140 Strength at Break MPa17.9 21.1 Elongation at Break % 580 470 Hardness Shore D D 37.8 40.3Glass transition ° C. −21.6 −18 temperature

What is claimed is:
 1. A butene-1 polymer composition having a MFR valueof from 100 to 300 g/10 min. measured according to ISO 1133 at 190° C.with a load of 2.16 kg, and comprising: A) a butene-1 homopolymer or acopolymer of butene-1 with one or more comonomers selected from thegroup consisting of ethylene and higher alpha-olefins, having acopolymerized comonomer content (C_(A)) of up to 5% by mole and B) acopolymer of butene-1 with one or more comonomers selected from thegroup consisting of ethylene and higher alpha-olefins, having acopolymerized comonomer content (C_(B)) of from 6% to 20% by mole;wherein the composition having a total copolymerized comonomer contentfrom 4% to 15% by mole referred to the sum of A) and B), and a contentof fraction soluble in xylene at 0° C. of 75% by weight or lessdetermined on the total weight of A) and B).
 2. The butene-1 polymercomposition of claim 1, wherein from 30% to 70% by weight of A) and from30% to 70% by weight of B), referred to the total weight of A) and B).3. The butene-1 polymer composition of claim 1, having DH TmII values offrom 4 to 15 J/g, measured with a scanning speed corresponding to 10°C./min.
 4. The butene-1 polymer composition of claim 1, having a Mw/Mnvalue, where Mw is the weight average molar mass and Mn is the numberaverage molar mass, both measured by GPC, equal to or lower than 3.5. 5.The butene-1 polymer composition of claim 1, having a Mz value, measuredby GPC, of 90,000 g/mol or higher.
 6. The butene-1 polymer compositionof claim 1, having a Mw value equal to or greater than 50,000 g/mol. 7.A process for preparing the butene-1 polymer composition of claim 1,comprising; at least two sequential stages, carried out in two or morereactors connected in series, wherein components A) and B) are preparedin separate subsequent stages, operating in each stage, except the firststage, in the presence of the polymer formed and the catalyst used inthe preceding stage.
 8. The process of claim 7, carried out in thepresence of a metallocene catalyst obtainable by contacting: astereorigid metallocene compound; an alumoxane or a compound capable offorming an alkyl metallocene cation; and, optionally, an organo aluminumcompound.
 9. A manufactured article comprising; the butene-1 polymercomposition of claim
 1. 10. The manufactured article of claim 9 whereinthe manufactured articles is a film or a fiber.
 11. A hot-melt adhesivecomposition comprising: the butene-1 polymer composition of claim 1.